Heavy oligomer compositions of a selective 1-hexene and 1-octene catalyst

ABSTRACT

A C 10  hydrocarbon composition of greater than 55 wt. % C 10  mono-olefins containing from 11 to 45 wt. % 1-decene, at least 0.5 wt. % 2-butyl-1-hexene, at least 1 wt. % 3-propyl-1-heptene, from 0.5 to 12 wt. % 4-ethyl-1-octene, at least 4 wt. % 4-penten-1-yl-cyclopentane, and from 2 to 40 wt. % 5-methyl-1-nonene. A C 12  hydrocarbon composition of greater than 60 wt. % C 12  mono-olefins containing at least 8 wt. % 1-dodecene and at least 0.5 wt. % 6-hepten-1-yl-cyclopentane, and the composition also containing heptylcyclopentane and n-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from 0:3:1 to 8:1. A C 14  hydrocarbon composition of greater than 60 wt. % C 14  mono-olefins containing at least 12 wt. % 1-tetradecene and at least 0.5 wt. % 8-nonen-1-yl-cyclopentane, and the composition also containing from 3 to 30 wt. % of n-tetradecane and nonylcyclopentane.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 63/241,121, filed on Sep. 7, 2021, the disclosure ofwhich is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure relates generally to C₁₀+ olefins, and moreparticularly, relates to linear, branched, and cyclic C₁₀-C₁₄ olefinsproduced from ethylene oligomerization processes.

BACKGROUND OF THE INVENTION

Many hydrocarbons heavier than 1-octene are produced in ethyleneoligomerization processes. However, isolation and identification ofvarious mono-olefins and hydrocarbons in the C₁₀-C₁₄ range aredifficult. It would be beneficial to determine the compositionalbreakdown of C₁₀-C₁₄ mono-olefins and hydrocarbons in the oligomerproduct resulting from ethylene oligomerization processes. Accordingly,it is to these ends that the present invention is generally directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described herein. This summary is notintended to identify required or essential features of the claimedsubject matter. Nor is this summary intended to be used to limit thescope of the claimed subject matter.

Olefin compositions are described herein. A first composition consistentwith this disclosure can comprise at least 55 wt. % C₁₀ mono-olefins. Inthe first composition, the C₁₀ mono-olefins can comprise from 11 to 45wt. % 1-decene, at least 0.5 wt. % 2-butyl-1-hexene, at least 1 wt. %3-propyl-1-heptene, from 0.5 to 12 wt. % 4-ethyl-1-octene, at least 4wt. % 4-penten-1-yl-cyclopentane, and from 2 to 40 wt. %5-methyl-1-nonene. As one of skill in the art would readily recognize,the total of these and other components does not exceed 100 wt. %.

A second composition provided herein can comprise at least 60 wt. % C₁₂mono-olefins. In the second composition, the C₁₂ mono-olefins cancomprise at least 8 wt. % 1-dodecene and at least 0.5 wt. %6-hepten-1-yl-cyclopentane, and the composition can compriseheptylcyclopentane and n-dodecane at a weight ratio ofheptylcyclopentane to n-dodecane from 0:3:1 to 8:1.

A third composition provided herein can comprise at least 60 wt. % C₁₄mono-olefins. In the third composition, the C₁₄ mono-olefins cancomprise at least 12 wt. % 1-tetradecene and at least 0.5 wt. %8-nonen-1-yl-cyclopentane, and the composition can comprise a total offrom 3 to 30 wt. % of n-tetradecane and nonylcyclopentane.

Also described herein are C₁₀-C₁₂ compositions, which can comprisegenerally from 30 to 60 wt. % of the first composition and from 38 to 68wt. % of the second composition, and C₁₂-C₁₄ compositions, which cancomprise generally from 45 to 85 wt. % of the second composition andfrom 20 to 50 wt. % of the third composition. Similarly, a C₁₀-C₁₄composition consistent with this disclosure often can contain from 25 to47 wt. % of the first composition, from 30 to 55 wt. % of the secondcomposition, and from 12 to 35 wt. % of the third composition. In likemanner, a C₁₀-C₁₈ composition provided herein can comprise from 15 to 40wt. % of the first composition, from 19 to 40 wt. % of the secondcomposition, from 7 to 25 wt. % of the third composition, and from 18 to40 wt. % of C₁₆-C₁₈ hydrocarbons.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations can be provided inaddition to those set forth herein. For example, certain aspects can bedirected to various feature combinations and sub-combinations describedin the detailed description.

Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter can be described such that,within particular aspects, a combination of different features can beenvisioned. For each and every aspect and/or feature disclosed herein,all combinations that do not detrimentally affect the designs,compositions, processes, and/or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect and/or feature disclosed herein can be combined to describeinventive features consistent with the present disclosure.

In this disclosure, while compositions, processes/methods, and systemsare described in terms of “comprising” various materials, steps, andcomponents, the compositions, processes/methods, and systems also can“consist essentially of” or “consist of” the various materials, steps,or components, unless stated otherwise. The terms “a,” “an,” and “the”are intended to include plural alternatives, e.g., at least one, unlessotherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound or group disclosed herein, any name orstructure presented is intended to encompass all conformational isomers,regioisomers, stereoisomers, and mixtures thereof that can arise from aparticular set of substituents, unless otherwise specified. The name orstructure also encompasses all enantiomers, diastereomers, and otheroptical isomers (if there are any), whether in enantiomeric or racemicforms, as well as mixtures of stereoisomers, as would be recognized by askilled artisan, unless otherwise specified. For example, a generalreference to hexene (or hexenes) includes all linear or branched,acyclic or cyclic, hydrocarbon compounds having six carbon atoms and 1carbon-carbon double bond; a general reference to pentane includesn-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and a generalreference to a butyl group includes an n-butyl group, a sec-butyl group,an iso-butyl group, and a t-butyl group.

The terms “contacting” and “combining” are used herein to describecompositions, processes/methods, and systems in which the materials arecontacted or combined together in any order, in any manner, and for anylength of time, unless otherwise specified. For example, the materialscan be blended, mixed, slurried, dissolved, reacted, treated,impregnated, compounded, or otherwise contacted or combined in someother manner or by any suitable method or technique.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon).

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).

The term “olefin” whenever used in this specification and claims refersto hydrocarbons that have at least one carbon-carbon double bond that isnot part of an aromatic ring or an aromatic ring system. The term“olefin” includes aliphatic and aromatic, cyclic and acyclic, and/orlinear and branched hydrocarbons having at least one carbon-carbondouble bond that is not part of an aromatic ring or ring system unlessspecifically stated otherwise. Olefins having only one, only two, onlythree, etc., carbon-carbon double bonds can be identified by use of theterm “mono,” “di,” “tri,” etc., within the name of the olefin. Theolefins can be further identified by the position of the carbon-carbondouble bond(s).

The term “alpha olefin” as used herein refers to any olefin that has acarbon-carbon double bond between the first and second carbon atom ofthe longest contiguous chain of carbon atoms. The term “alpha olefin”includes linear and branched alpha olefins and alpha olefins which canhave more than one non-aromatic carbon-carbon double bond, unlessexpressly stated otherwise. The term “normal alpha olefin” as usedherein refers to a linear aliphatic hydrocarbon mono-olefin having acarbon-carbon double bond between the first and second carbon atoms. Theterm “linear internal olefin” as used herein refers to a linearaliphatic hydrocarbon mono-olefin having a double bond that is notbetween the first and second carbon atom.

The term oligomer refers to a product that contains from 2 to 20 monomerunits. The terms “oligomerization product” and “oligomer product”include all products made by the “oligomerization” process, includingthe “oligomers” and products which are not “oligomers” (e.g., productswhich contain more than 20 monomer units, or solid polymer), but excludeother non-oligomer components of an oligomerization reaction zoneeffluent stream, such as unreacted ethylene, organic reaction medium,and hydrogen, amongst other components.

Several types of ranges are disclosed in the present invention. When arange of any type is disclosed or claimed, the intent is to disclose orclaim individually each possible number that such a range couldreasonably encompass, including end points of the range as well as anysub-ranges and combinations of sub-ranges encompassed therein. Forexample, when a chemical moiety having a certain number of carbon atomsis disclosed or claimed, the intent is to disclose or claim individuallyevery possible number that such a range could encompass, consistent withthe disclosure herein. For example, the disclosure that a compound is aC₁ to C₁₈ hydrocarbon, or in alternative language, a hydrocarbon havingfrom 1 to 18 carbon atoms, as used herein, refers to a compound that canhave 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18carbon atoms, as well as any range between these two numbers (forexample, a C₁₀ to C₁₄ hydrocarbon), and also including any combinationof ranges between these two numbers (for example, a C₂ to C₄ and a C₁₀to C₁₈ hydrocarbon). Likewise, all other ranges disclosed herein shouldbe interpreted in a manner similar to this example.

In general, an amount, size, formulation, parameter, range, or otherquantity or characteristic is “about” or “approximate” whether or notexpressly stated to be such. Whether or not modified by the term “about”or “approximately,” the claims include equivalents to the quantities orcharacteristics.

Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of theinvention, the typical methods and materials are herein described.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to C₁₀+ olefins, such aslinear, branched, and cyclic C₁₀-C₁₄ olefins produced from ethyleneoligomerization processes. C₁₀+ olefins can be produced by contactingethylene and a chromium-based catalyst system to form an oligomerproduct containing 1-hexene, 1-octene, and C₁₀+ olefins, andsubsequently separating or fractionating the oligomer product into C₆olefins such as 1-hexene, C₈ olefins such as 1-octene, and C₁₀+ olefins.

The C₁₀+ olefins can be further separated or fractionated into a C₁₀composition, a C₁₂ composition, a C₁₄ composition, and C₁₆ and/or C₁₈fractions. Any suitable technique can be used, such as vacuumdistillation.

General information on chromium-based catalyst systems, ethyleneoligomerization processes, and isolation of oligomer product fractionscan be found, for instance, in U.S. Pat. Nos. 10,493,422, 10,464,862,and 10,435,336.

C₁₀ Compositions

A first composition disclosed herein can comprise at least 55 wt. % C₁₀mono-olefins. In some aspects, the first composition can comprise atleast 60 wt. % C₁₀ mono-olefins, at least 65 wt. % C₁₀ mono-olefins, atleast 70 wt. % C₁₀ mono-olefins, at least 80 wt. % C₁₀ mono-olefins, orat least 85 wt. % C₁₀ mono-olefins. Therefore, illustrative andnon-limiting ranges for the amount of C₁₀ mono-olefins in thecomposition can include from 55 to 98 wt. %, from 70 to 95 wt. %, from85 to 95 wt. %, from 55 to 85 wt. %, from 60 to 92 wt. %, or from 65 to85 wt. %, and the like.

In the first composition, the C₁₀ mono-olefins can comprise from 11 to45 wt. % 1-decene, at least 0.5 wt. % 2-butyl-1-hexene, at least 1 wt. %3-propyl-1-heptene, from 0.5 to 12 wt. % 4-ethyl-1-octene, at least 4wt. % 4-penten-1-yl-cyclopentane, and from 2 to 40 wt. %5-methyl-1-nonene. While not limited thereto, the amount of 1-decene,based on the total C₁₀ mono-olefins in the composition, often can rangefrom 12 to 42 wt. %. In one aspect, for example, the C₁₀ mono-olefinscan contain from 12 to 30 wt. % 1-decene, while in another aspect, from15 to 38 wt. %, and from 17 to 35 wt. % in yet another aspect, and from20 to 30 wt. % in still another aspect.

At least 0.5 wt. % of the C₁₀ mono-olefins in the first composition canbe 2-butyl-1-hexene. Typical ranges for the amount of 2-butyl-1-hexenein the C₁₀ mono-olefins include, but are not limited to, from 0.5 to 12wt. %, from 0.75 to 12 wt. %, from 1 to 8 wt. %, or from 2 to 6 wt. %.Additionally, the C₁₀ mono-olefins in the first composition also containat least 1 wt. % 3-propyl-1-heptene. Based on C₁₀ mono-olefins, theamount of 3-propyl-1-heptene can range from 1 to 27 wt. %;alternatively, from 3 to 25 wt. %; alternatively, from 5 to 22 wt. %; oralternatively, from 7 to 17 wt. %. The first composition also cancontain from 0.5 to 10 wt. % 4-ethyl-1-octene, based on the C₁₀mono-olefins. For instance, the first composition can contain, based onthe C₁₀ mono-olefins, from 0.75 to 7 wt. %, from 0.75 to 5 wt. %, from 1to 5 wt. %, or from 1 to 4 wt. %, of 4-ethyl-1-octene. Further, thefirst composition can contain at least 4 wt. %4-penten-1-yl-cyclopentane, with typical ranges for the amount of4-penten-1-yl-cyclopentane including from 4 to 40 wt. %, from 4 to 37wt. %, from 5 to 34 wt. %, from 7 to 30 wt. %, or from 10 to 25 wt. %.As above, these weight percentages are based on the amount of C₁₀mono-olefins in the first composition. Lastly, the first compositionalso can contain, based on C₁₀ mono-olefins, from 2 to 40 wt. %5-methyl-1-nonene. Other suitable ranges for the amount of5-methyl-1-nonene include, but are not limited to, from 2 to 38 wt. %,from 4 to 40 wt. %, from 4 to 33 wt. %, from 6 to 33 wt. %, or from 10to 28 wt. %.

In the first composition, the weight ratio of(2-butyl-1-hexene+3-propyl-1-heptene+4-ethyl-1-octene+5-methyl-1-nonene)to 1-decene typically falls within a range from 0.2:1 to 10:1. In oneaspect, the ratio is in a range from 0.3:1 to 8:1, while in anotheraspect, the ratio is in a range from 0.35:1 to 6:1, and in yet anotheraspect, the ratio is in a range from 0.4:1 to 5:1, and in still anotheraspect, the ratio is in a range from 0.8:1 to 5:1. Additionally oralternatively, the weight ratio of 4-penten-1-yl-cyclopentane to1-decene in the first composition often ranges from 0:1:1 to 3:1, suchas from 0.2:1 to 2:1, from 0.2:1 to 1.2:1, from 0.3:1 to 1.5:1, from0.3:1 to 1:1, or from 0.4:1 to 0.9:1. Additionally or alternatively, theweight ratio of(2-butyl-1-hexene+3-propyl-1-heptene+4-ethyl-1-octene+5-methyl-1-nonene)to 4-penten-1-yl-cyclopentane can range from 0.1:1 to 12:1, and moreoften, can range from 0.4:1 to 10:1, from 4:1 to 10:1, from 6:1 to 9:1,from 0.3:1 to 4:1, or from 0.4:1 to 3:1.

Optionally, the C₁₀ mono-olefins in first composition also can furthercomprise 2-ethyl-1-octene and/or 3-methyl-1-nonene. When present, basedon the C₁₀ mono-olefins, the first composition can comprise from 0.3 to8 wt. %, from 0.5 to 5 wt. %, from 1 to 5 wt. %, or from 0.8 to 4 wt. %of 2-ethyl-1-octene. Likewise, when present, the 3-methyl-1-nonene canbe present in an amount from greater than 0 to 10 wt. %, from greaterthan 0 to 8 wt. %, from greater than 0 to 6 wt. %, or from 2 to 7 wt. %,based on C₁₀ mono-olefins.

In addition to C₁₀ mono-olefins, the first composition also can containnon-olefinic hydrocarbons, such as alkanes like n-decane andpentylcyclopentane. The amount of pentylcyclopentane in the compositioncan range from 1 to 20 wt. %, from 2 to 18 wt. %, from 3 to 15 wt. %,from 5 to 13 wt. %, or from 7 to 13 wt. %, although not limited thereto.In general, the first composition is predominantly C₁₀ hydrocarbons(inclusive of C₁₀ mono-olefins), and often the first compositioncontains at least 90 wt. % C₁₀ hydrocarbons, at least 95 wt. % C₁₀hydrocarbons, at least 96 wt. % C₁₀ hydrocarbons, at least 97 wt. % C₁₀hydrocarbons, at least 98 wt. % C₁₀ hydrocarbons, or at least 99 wt. %C₁₀ hydrocarbons.

C₁₂ Compositions

A second composition disclosed herein can comprise at least 60 wt. % C₁₂mono-olefins. In some aspects, the second composition can comprise atleast 65 wt. % C₁₂ mono-olefins, at least 70 wt. % C₁₂ mono-olefins, atleast 75 wt. % C₁₂ mono-olefins, at least 80 wt. % C₁₂ mono-olefins, orat least 85 wt. % C₁₂ mono-olefins. Therefore, illustrative andnon-limiting ranges for the amount of C₁₂ mono-olefins in the secondcomposition can include from 60 to 99 wt. %, from 60 to 95 wt. %, from62 to 97 wt. %, from 70 to 98 wt. %, from 70 to 95 wt. %, from 75 to 95wt. %, from 80 to 97.5 wt. %, from 80 to 95 wt. %, or from 85 to 99 wt.%, and the like.

In the second composition, the C₁₂ mono-olefins can comprise at least 8wt. % 1-dodecene and at least 0.5 wt. % 6-hepten-1-yl-cyclopentane, andthe second composition also can comprise heptylcyclopentane andn-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from0:3:1 to 8:1. While not limited thereto, the amount of 1-dodecene, basedon the total C₁₂ mono-olefins in the composition, often can range from 8to 40 wt. %. In one aspect, for example, the C₁₂ mono-olefins cancontain from 9 to 35 wt. % 1-dodecene, while in another aspect, from 10to 33 wt. %, and from 12 to 29 wt. % in yet another aspect, and from 13to 23 wt. % in still another aspect.

At least 22 wt. % of the C₁₂ mono-olefins in the second composition canbe non-cyclic branched C₁₂ mono-olefins. Representative non-cyclicbranched C₁₂ mono-olefins can include, but are not limited to,5-methyl-1-undecene, 7-methyl-1-undecene, 4-ethyl-1-decene,6-ethyl-1-decene, 3-propyl-1-nonene, 5-propyl-1-nonene,2-butyl-1-octene, 3-butyl-1-octene, 4-butyl-1-octene, and the like, aswell as any combination thereof. In some aspects, from 27 to 90 wt. % ofthe C₁₂ mono-olefins in the second composition are non-cyclic branchedC₁₂ mono-olefins, such as from 22 to 90 wt. %, from 29 to 88 wt. %, from60 to 86 wt. %, from 60 to 80 wt. %, from 35 to 85 wt. %, from 33 to 50wt. %, or from 33 to 40 wt. %, and the like.

At least 0.5 wt. % of the C₁₂ mono-olefins in the second composition canbe 6-hepten-1-yl-cyclopentane. Typical ranges for the amount of6-hepten-1-yl-cyclopentane in the C₁₂ mono-olefins include, but are notlimited to, from 0.5 to 40 wt. %, from 1 to 35 wt. %, from 2 to 40 wt.%, from 2 to 32 wt. %, from 3 to 20 wt. %, or from 4 to 15 wt. %.

In the second composition, the weight ratio of 1-dodecene to6-hepten-1-yl-cyclopentane typically falls within a range from 0:4:1 to12:1. In one aspect, the ratio is in a range from 0.6:1 to 10:1, whilein another aspect, the ratio is in a range from 0.6:1 to 4:1, and inanother aspect, the ratio is in a range from 0.9:1 to 8:1, and in yetanother aspect, the ratio is in a range from 0.9:1 to 6:1, and in stillanother aspect, the ratio is in a range from 1.5:1 to 4:1. Additionallyor alternatively, the weight ratio of non-cyclic branched C₁₂mono-olefins to 6-hepten-1-yl-cyclopentane in the second compositionoften ranges from 0.4:1 to 55:1, such as from 0.6:1 to 50:1, from 15:1to 45:1, from 30:1 to 45:1, from 0.6:1 to 30:1, from 0.6:1 to 15:1, orfrom 0.9:1 to 11:1.

In addition to C₁₂ mono-olefins, the second composition also can containnon-olefinic hydrocarbons, such as alkanes like heptylcyclopentane andn-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from0:3:1 to 8:1. While not limited thereto, the amount of n-dodecane in thesecond composition can range from 0.25 to 18 wt. %, from 0.5 to 16 wt.%, from 0.5 to 10 wt. %, from 0.75 to 8 wt. %, from 1 to 12 wt. %, from8 to 14 wt. %, or from 0.75 to 10 wt. %. The amount ofheptylcyclopentane in the composition can be range from 0.25 to 25 wt.%, from 0.5 to 23 wt. %, from 1 to 23 wt. %, from 3 to 20 wt. %, from 1to 18 wt. %, or from 3 to 10 wt. %, although not limited thereto. Theweight ratio of heptylcyclopentane to n-dodecane can vary from 0:3:1 to8:1, and other suitable range include, but are not limited to, from0:3:1 to 6:1, from 0.3:1 to 3:1, from 0.5:1 to 5:1, from 0.5:1 to 2:1,from 0.8:1 to 8:1, from 0.8:1 to 4:1, or from 0.8:1 to 1.8:1, and thelike.

In general, the second composition is predominantly C₁₂ hydrocarbons(inclusive of C₁₂ mono-olefins), and often the second compositioncontains at least 90 wt. % C₁₂ hydrocarbons, at least 95 wt. % C₁₂hydrocarbons, at least 96 wt. % C₁₂ hydrocarbons, at least 97 wt. % C₁₂hydrocarbons, at least 98 wt. % C₁₂ hydrocarbons, or at least 99 wt. %C₁₂ hydrocarbons.

C₁₄ Compositions

A third composition disclosed herein can comprise at least 60 wt. % C₁₄mono-olefins. In some aspects, the third composition can comprise atleast 65 wt. % C₁₄ mono-olefins, at least 70 wt. % C₁₄ mono-olefins, atleast 80 wt. % C₁₄ mono-olefins, or at least 85 wt. % C₁₄ mono-olefins.Therefore, illustrative and non-limiting ranges for the amount of C₁₄mono-olefins in the composition can include from 55 to 98 wt. %, from 60to 99 wt. %, from 60 to 80 wt. %, from 68 to 96 wt. %, from 70 to 95 wt.%, from 75 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 97.5 wt. %,and the like.

In the third composition, the C₁₄ mono-olefins can comprise at least 12wt. % 1-tetradecene and at least 0.5 wt. % 8-nonen-1-yl-cyclopentane,and the third composition also can comprise a total of from 3 to 30 wt.% of n-tetradecane and nonylcyclopentane. While not limited thereto, theamount of 1-tetradecene, based on the total C₁₄ mono-olefins in thecomposition, often can range from 12 to 50 wt. %. In one aspect, forexample, the C₁₄ mono-olefins can contain from 14 to 45 wt. %1-tetradecene, while in another aspect, from 15 to 40 wt. %, and from 16to 38 wt. % in another aspect, from 18 to 36 wt. % in yet anotheraspect, and from 20 to 35 wt. % in still another aspect.

At least 22 wt. % of the C₁₄ mono-olefins in the third composition canbe non-cyclic branched C₁₄ mono-olefins. Representative non-cyclicbranched C₁₄ mono-olefins can include, but are not limited to,7-methyl-1-tridecene, 6-ethyl-1-dodecene, 5-propyl-1-undecene,4-butyl-1-decene, 3-pentyl-1-nonene, and the like, as well as anycombination thereof. In some aspects, from 25 to 85 wt. % of the C₁₄mono-olefins in the third composition are non-cyclic branched C₁₄mono-olefins, such as from 30 to 80 wt. %, from 45 to 80 wt. %, from 55to 70 wt. %, from 36 to 78 wt. %, or from 50 to 75 wt. %, and the like.

At least 0.5 wt. % of the C₁₄ mono-olefins in the third composition canbe 8-nonen-1-yl-cyclopentane. Typical ranges for the amount of8-nonen-1-yl-cyclopentane in the C₁₄ mono-olefins include, but are notlimited to, from 0.5 to 30 wt. %, from 0.75 to 28 wt. %, from 1.5 to 26wt. %, from 2 to 24 wt. %, or from 5 to 15 wt. %.

In the third composition, the weight ratio of 1-tetradecene to8-nonen-1-yl-cyclopentane typically falls within a range from 0:5:1 to15:1. In one aspect, the ratio is in a range from 0.75:1 to 12:1, whilein another aspect, the ratio is in a range from 1:1 to 10:1, and in yetanother aspect, the ratio is in a range from 1.5:1 to 9:1, and in stillanother aspect, the ratio is in a range from 2:1 to 8:1. Additionally oralternatively, the weight ratio of non-cyclic branched C₁₄ mono-olefinsto 8-nonen-1-yl-cyclopentane in the third composition often ranges from0.5:1 to 50:1, from 0.75:1 to 45:1, from 15:1 to 42:1, from 30:1 to40:1, from 0.75:1 to 30:1, from 1:1 to 15:1, or from 1.25:1 to 10:1.

In addition to C₁₄ mono-olefins, the third composition also can containnon-olefinic hydrocarbons, such as alkanes like n-tetradecane andnonylcyclopentane at a total amount of from 3 to 30 wt. %. While notlimited thereto, the amount of n-tetradecane in the third compositioncan range from 0.5 to 18 wt. %, from 1 to 16 wt. %, from 2 to 12 wt. %,from 1.25 to 15 wt. %, or from 3 to 9 wt. %. The amount ofnonylcyclopentane in the composition can range from 0.5 to 22 wt. %,from 1 to 20 wt. %, from 1 to 14 wt. %, from 1.25 to 18 wt. %, or from 3to 10 wt. %, although not limited thereto. The total amount ofn-tetradecane and nonylcyclopentane in the third composition can varyfrom 3 to 30 wt. %, and other suitable range include, but are notlimited to, from 3 to 28 wt. %, from 3 to 26 wt. %, from 4 to 28 wt. %,from 5 to 25 wt. %, or from 6 to 20 wt. %, and the like.

In general, the third composition is predominantly C₁₄ hydrocarbons(inclusive of C₁₄ mono-olefins), and often the third compositioncontains at least 90 wt. % C₁₄ hydrocarbons, at least 95 wt. % C₁₄hydrocarbons, at least 96 wt. % C₁₄ hydrocarbons, at least 97 wt. % C₁₄hydrocarbons, at least 98 wt. % C₁₄ hydrocarbons, or at least 99 wt. %C₁₄ hydrocarbons.

Compositions Containing C₁₀ to C₁₈ Olefins

Another composition consistent with aspects of this invention can bereferred to as a C₁₀-C₁₂ composition, and this composition generally cancontain from 30 to 60 wt. % of the first composition (and any of thefeatures of the first composition described herein) and from 38 to 68wt. % of the second composition (and any of the features of the secondcomposition described herein). Other amounts of the first composition inthe C₁₀-C₁₂ composition can be present, thus for instance, the C₁₀-C₁₂composition can contain from 35 to 55 wt. %, or from 40 to 50 wt. %, ofthe first composition. Additionally or alternatively, the C₁₀-C₁₂composition can contain from 43 to 63 wt. %, or from 48 to 58 wt. %, ofthe second composition. In general, the C₁₀-C₁₂ composition ispredominantly comprised of the first composition and the secondcomposition. Accordingly, the first composition and the secondcomposition, collectively, can represent at least 90 wt. %, at least 95wt. %, at least 97 wt. %, at least 98 wt. %, at least 99 wt. %, or atleast 99.5 wt. %, of the C₁₀-C₁₂ composition.

Illustrative and non-limiting ranges for the amount of C₁₀₋₁₂mono-olefins in the C₁₀₋₁₂ composition can include from 60 to 99 wt. %,from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. %, andthe like. Similar to the first composition and the second composition,the C₁₀-C₁₂ composition also can contain, in addition to C₁₀-C₁₂mono-olefins, non-olefinic hydrocarbons such as alkanes. In general, theC₁₀-C₁₂ composition is predominantly C₁₀-C₁₂ hydrocarbons, and often theC₁₀-C₁₂ composition contains at least 90 wt. % C₁₀-C₁₂ hydrocarbons, atleast 95 wt. % C₁₀-C₁₂ hydrocarbons, at least 96 wt. % C₁₀-C₁₂hydrocarbons, at least 97 wt. % C₁₀-C₁₂ hydrocarbons, at least 98 wt. %C₁₀-C₁₂ hydrocarbons, or at least 99 wt. % C₁₀-C₁₂ hydrocarbons.

Another composition consistent with aspects of this invention can bereferred to as a C₁₂-C₁₄ composition, and this composition generally cancontain from 45 to 85 wt. % of the second composition (and any of thefeatures of the second composition described herein) and from 20 to 50wt. % of the third composition (and any of the features of the thirdcomposition described herein). Other amounts of the second compositionin the C₁₂-C₁₄ composition can be present, thus for instance, theC₁₂-C₁₄ composition can contain from 55 to 75 wt. %, or from 60 to 70wt. %, of the second composition. Additionally or alternatively, theC₁₂-C₁₄ composition can contain from 25 to 45 wt. %, or from 30 to 40wt. %, of the third composition. In general, the C₁₂-C₁₄ composition ispredominantly comprised of the second composition and the thirdcomposition. Accordingly, the second composition and the thirdcomposition, collectively, can represent at least 90 wt. %, at least 95wt. %, at least 97 wt. %, at least 98 wt. %, at least 99 wt. %, or atleast 99.5 wt. %, of the C₁₂-C₁₄ composition.

Illustrative and non-limiting ranges for the amount of C₁₂-14mono-olefins in the C₁₂-14 composition can include from 60 to 99 wt. %,from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. %, andthe like. Similar to the second composition and the third composition,the C₁₂-C₁₄ composition also can contain, in addition to C₁₂-C₁₄mono-olefins, non-olefinic hydrocarbons such as alkanes. In general, theC₁₂-C₁₄ composition is predominantly C₁₂-C₁₄ hydrocarbons, and often theC₁₂-C₁₄ composition contains at least 90 wt. % C₁₂-C₁₄ hydrocarbons, atleast 95 wt. % C₁₂-C₁₄ hydrocarbons, at least 96 wt. % C₁₂-C₁₄hydrocarbons, at least 97 wt. % C₁₂-C₁₄ hydrocarbons, at least 98 wt. %C₁₂-C₁₄ hydrocarbons, or at least 99 wt. % C₁₂-C₁₄ hydrocarbons.

Yet another composition consistent with aspects of this invention can bereferred to as a C₁₀-C₁₄ composition, and this composition generally cancontain from 25 to 47 wt. % of the first composition (and any of thefeatures of the first composition described herein), from 30 to 55 wt. %of the second composition (and any of the features of the secondcomposition described herein), and from 12 to 35 wt. % of the thirdcomposition (and any of the features of the third composition describedherein). Other amounts of the first composition in the C₁₀-C₁₄composition can be present, thus for instance, the C₁₀-C₁₄ compositioncan contain from 30 to 42 wt. %, or from 33 to 39 wt. %, of the firstcomposition. Additionally or alternatively, the C₁₀-C₁₄ composition cancontain from 35 to 47 wt. %, or from 38 to 44 wt. %, of the secondcomposition. Additionally or alternatively, the C₁₀-C₁₄ composition cancontain from 15 to 27 wt. %, or from 18 to 24 wt. %, of the thirdcomposition. In general, the C₁₀-C₁₄ composition is predominantlycomprised of the first composition, the second composition, and thethird composition. Accordingly, the first composition, the secondcomposition, and the third composition, collectively, can represent atleast 90 wt. %, at least 95 wt. %, at least 97 wt. %, at least 98 wt. %,at least 99 wt. %, or at least 99.5 wt. %, of the C₁₀-C₁₄ composition.

Illustrative and non-limiting ranges for the amount of C₁₀₋₁₄mono-olefins in the C₁₀₋₁₄ composition can include from 60 to 99 wt. %,from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. %, andthe like. Similar to the first, second, and third compositions, theC₁₀-C₁₄ composition also can contain, in addition to C₁₀-C₁₄mono-olefins, non-olefinic hydrocarbons such as alkanes. In general, theC₁₀-C₁₄ composition is predominantly C₁₀-C₁₄ hydrocarbons, and often theC₁₀-C₁₄ composition contains at least 90 wt. % C₁₀-C₁₄ hydrocarbons, atleast 95 wt. % C₁₀-C₁₄ hydrocarbons, at least 96 wt. % C₁₀-C₁₄hydrocarbons, at least 97 wt. % C₁₀-C₁₄ hydrocarbons, at least 98 wt. %C₁₀-C₁₄ hydrocarbons, or at least 99 wt. % C₁₀-C₁₄ hydrocarbons.

Still another composition consistent with aspects of this invention canbe referred to as a C₁₀-C₁₈ composition, and this composition generallycan contain from 15 to 40 wt. % of the first composition (and any of thefeatures of the first composition described herein), from 19 to 40 wt. %of the second composition (and any of the features of the secondcomposition described herein), from 7 to 25 wt. % of the thirdcomposition (and any of the features of the third composition describedherein), and from 18 to 40 wt. % of C₁₆-C₁₈ hydrocarbons. Other amountsof the first composition in the C₁₀-C₁₈ composition can be present, thusfor instance, the C₁₀-C₁₈ composition can contain from 19 to 35 wt. %,or from 22 to 30 wt. %, of the first composition. Additionally oralternatively, the C₁₀-C₁₈ composition can contain from 23 to 36 wt. %,or from 27 to 33 wt. %, of the second composition. Additionally oralternatively, the C₁₀-C₁₈ composition can contain from 10 to 22 wt. %,or from 13 to 19 wt. %, of the third composition. Additionally oralternatively, the C₁₀-C₁₈ composition can contain at least 22 wt. %, atleast 25 wt. %, from 22 to 36 wt. %, or from 25 to 33 wt. %, of C₁₆-C₁₈hydrocarbons. In general, the C₁₀-C₁₈ composition is predominantlycomprised of the first composition, the second composition, the thirdcomposition, and C₁₆-C₁₈ hydrocarbons.

Accordingly, the first composition, the second composition, the thirdcomposition, and C₁₆-C₁₈ hydrocarbons, collectively, can represent atleast 90 wt. %, at least 95 wt. %, at least 97 wt. %, at least 98 wt. %,at least 99 wt. %, or at least 99.5 wt. %, of the C₁₀-C₁₈ composition.

Illustrative and non-limiting ranges for the amount of C₁₀₋₁₈mono-olefins in the C₁₀₋₁₈ composition can include from 60 to 99 wt. %,from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. %, andthe like. Similar to the first, second, and third compositions, theC₁₀-C₁₈ composition also can contain, in addition to C₁₀-C₁₈mono-olefins, non-olefinic hydrocarbons such as alkanes. In general, theC₁₀-C₁₈ composition is predominantly C₁₀-C₁₈ hydrocarbons, and often theC₁₀-C₁₈ composition contains at least 90 wt. % C₁₀-C₁₈ hydrocarbons, atleast 95 wt. % C₁₀-C₁₈ hydrocarbons, at least 96 wt. % C₁₀-C₁₈hydrocarbons, at least 97 wt. % C₁₀-C₁₈ hydrocarbons, at least 98 wt. %C₁₀-C₁₈ hydrocarbons, or at least 99 wt. % C₁₀-C₁₈ hydrocarbons.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, modifications, and equivalentsthereof which, after reading the description herein, can suggestthemselves to one of ordinary skill in the art without departing fromthe spirit of the present invention or the scope of the appended claims.

Ethylene Oligomerization Experiment 1 was used to produce an oligomerproduct and followed this procedure: In a dry box, a 20-mL glass vialwas charged with a pre-catalyst (5 μmol) (a N²-phosphinyl guanidinechromium(III) trichloride tetrahydrofuran complex), 1 g ethylbenzene,and triethylaluminum (TEA) to achieve an Al:Cr molar ratio of 80:1. Theinitial pre-catalyst slurry became a homogenous solution while stirringfor 15 min. The solution was then treated with MMAO-21 (7 wt. % Al incyclohexane, Al:Cr of 400:1) and stirred for 105 min. The activatedpre-catalyst solution was then added to a 0.5-L glass charger containinga total of 200 mL of cyclohexane and 1-heptene (optionally, foranalytical differentiation) and transferred into an evacuated 0.5 Lstainless steel reactor heated to 70° C. Hydrogen (50 psig) was chargedinto the reactor followed by ethylene (875 psig). The reaction proceededto exotherm to the target temperature of 85° C. with ethylene being fedon-demand to maintain the desired reactor pressure. After 20-30 min, theoligomerization reaction was rapidly cooled to 30° C., and then theunreacted ethylene and hydrogen gas were vented. A 2-mL sample of theliquid sample was collected, filtered, and analyzed by GC-FID. The threeruns (one with heptene and two without) of Experiment 1 produced nominalsolids.

GC-FID data was collected on an Agilent Technologies 7890A instrumentequipped with a 50 m length Agilent DB-5 GC column with an innerdiameter of 0.32 mm and film thickness of 0.25 μm. The sample (0.05 μL)was syringe injected into the inlet with a split ratio of 25:1 at 300°C. using Ile as the carrier gas. The initial column temperature was 40°C. with a temperature ramp rate of 3° C./min up to 80° C., followed by a13° C./min ramp up to 300° C. and a 15 min hold time. Peak integrationwas performed manually and peak identification was made using authenticsamples.

Table 1 summarizes the oligomer distribution of the products formed fromEthylene Oligomerization Experiment 1 (with no heptene). The bulk of theheavy (>C₈) oligomers formed fell in the C₁₀ to C₁₄ range. The totalamount of C₁₀-C₁₄ products (7.65 g) was over twice that of the remainingheavier oligomers (3.06 g). Primary C₆ and C₈ products (total of 105.26g) were the vast majority of the oligomer product. C₁₀ and C₁₂ fractionswere produced in similar amounts, while the C₁₄ fraction was about halfthat of either C₁₀ or C₁₂.

The measured distribution in Table 2 summarizes the breakdown (in wt. %)of the C₁₀ fraction produced in Ethylene Oligomerization Experiment 1.The skewed cyclic and skewed linear columns are prophetic distributionsif cyclic mechanisms and linear mechanisms, respectively, were favored.While not wishing to be bound by the following theory, it is believedthat cyclic mechanisms are enhanced with higher ethylene conversions,higher 1-hexene/1-octene product ratios, higher oligomerizationtemperatures, and lower chromium contents in the reaction zone.Conversely, it is believed that lower oligomerization temperatures andhigher hydrogen contents in the reaction zone enhance linear mechanisms.

Table 3 summarizes four possible mechanisms that can possibly produce upto sixteen C₁₀ species from ethylene and 1-hexene or 1-octene.Unexpectedly, 3-methylnonane is unique to the linear dimerizationmechanism, while 5-methylnonane is unique to the linear trimerizationmechanism. While 4-penten-1-yl-cyclopentane and pentylcyclopentane alsoare unique to the linear trimerization mechanism as noted in Table 3, itis believed that these species also may be formed by ethylene insertioninto a chromium catalyst intermediate.

Several species from the measured distribution in Table 2 are reproducedin the inventive column of Table 4. The comparative column representsresults from Ethylene Oligomerization Experiment 2, an oligomerizationexperiment performed as described above, except that the chromiumpre-catalyst was (PNP)CrCl₃(THF) (PNP is Ph₂PN(iPr)PPh₂, where Ph isphenyl and iPr is isopropyl), the oligomerization temperature was 70°C., and no TEA was used. A lower temperature was used for thecomparative example to reduce the amount of polymer that was produced athigher temperatures. Unexpectedly, the inventive example (EthyleneOligomerization Experiment 1) had significantly less 1-decene andsignificantly more 4-penten-1-yl-cyclopentane and pentylcyclopentane.Interestingly, since higher oligomerization temperatures favor cyclicmechanisms, if the comparative example (Ethylene OligomerizationExperiment 2) was suitable for testing at the same (higher) temperatureas the inventive example, it is believed that even less4-penten-1-yl-cyclopentane and pentylcyclopentane would have beenproduced in the comparative example (based on the information in Tables2-3.

Referring now to the C₁₂ products, the measured distribution in Table 5summarizes the breakdown (in wt. %) of the C₁₂ fraction produced inEthylene Oligomerization Experiment 1. The skewed cyclic and skewedlinear columns are prophetic distributions if cyclic mechanisms andlinear mechanisms, respectively, were favored. Again, while not wishingto be bound by the following theory, it is believed that cyclicmechanisms are enhanced with higher ethylene conversions, higher1-hexene/1-octene product ratios, higher oligomerization temperatures,and lower chromium contents in the reaction zone. Conversely, it isbelieved that lower oligomerization temperatures and higher hydrogencontents in the reaction zone enhance linear mechanisms. The 1-dodecene,n-dodecane, heptylcyclopentane, and 6-hepten-1-ylcyclopentane specieswere conclusively identified and quantified by GC-MS (same GC method asabove, but a different analyzer). However, the other compounds in Table5 (e.g., non-cyclic branched C₁₂ mono-olefins and non-cyclic branchedC₁₂ alkanes) were lumped into related groups and their total wt. % wasestimated using GC-FID and comparative analysis, but the individualcompounds were not independently verified.

Table 6 summarizes five possible mechanisms that can possibly produce upto 21 C₁₂ species from ethylene and 1-hexene or 1-octene. It is believedthat a majority of the C₁₂ fraction (the non-cyclic branched C₁₂mono-olefins) were generated by the two metallacyclic pathways.Surprisingly, the metallacyclic trimerization pathway produced fourunique alkenes (6-dodecene, 5-methyl-1-undecene, 4-ethyl-1-decene,3-propyl-1-nonene) as well as the metallacyclic tetramerization(4-dodecene, 7-methyl-1-undecene, 6-ethyl-1-decene, 5-propyl-1-nonene).Further, unlike the C₁₀ fraction and C₁₄ fraction described herein, theC₁₂ fraction surprisingly appears to be predominantly generated through1-alkene/ethylene metallacyclization.

Several species from the measured distribution in Table 5 are reproducedin the inventive column of Table 7. The comparative column representsresults from Ethylene Oligomerization Experiment 2. Unexpectedly, theinventive example (Ethylene Oligomerization Experiment 1) hadsignificantly more 6-hepten-1-ylcyclopentane and heptylcyclopentane.Interestingly, since higher oligomerization temperatures favor cyclicmechanisms, if the comparative example (Ethylene OligomerizationExperiment 2) was suitable for testing at the same (higher) temperatureas the inventive example, it is believed that even less6-hepten-1-ylcyclopentane and heptylcyclopentane would have beenproduced in the comparative example (based on the information in Tables5-6.

Referring now to the C₁₄ products, the measured distribution in Table 8summarizes the breakdown (in wt. %) of the C₁₄ fraction produced inEthylene Oligomerization Experiment 1. The skewed cyclic and skewedlinear columns are prophetic distributions if cyclic mechanisms andlinear mechanisms, respectively, were favored. The 1-tetradecene,n-tetradecane, nonylcyclopentane, and 8-nonen-1-ylcyclopentane specieswere conclusively identified by GC-MS. However, the other compounds inTable 8 (e.g., non-cyclic branched C₁₄ mono-olefins and non-cyclicbranched C₁₄ alkanes) were lumped into related groups and their totalwt. % was estimated using GC-FID and comparative analysis, but theindividual compounds were not independently verified.

Table 9 summarizes four possible mechanisms that can possibly produce upto fourteen C₁₄ species from ethylene and 1-hexene or 1-octene. It isbelieved that a majority of the C₁₄ fraction (the non-cyclic branchedC₁₄ mono-olefins) was generated from metallacyclic tetramerization. Thenonylcyclopentane and 8-nonen-1-ylcyclopentane species appear to beformed exclusively from a linear mechanism.

Several species from the measured distribution in Table 8 are reproducedin the inventive column of Table 10. The comparative column representsresults from Ethylene Oligomerization Experiment 2. Unexpectedly, theinventive example (Ethylene Oligomerization Experiment 1) hadsignificantly more n-tetradecane, 8-nonen-1-ylcyclopentane, andnonylcyclopentane. Interestingly, since higher oligomerizationtemperatures favor cyclic mechanisms, if the comparative example(Ethylene Oligomerization Experiment 2) was suitable for testing at thesame (higher) temperature as the inventive example, it is believed thateven less n-tetradecane, 8-nonen-1-ylcyclopentane, and nonylcyclopentanewould have been produced in the comparative example (based on theinformation in Tables 8-9.

TABLE 1 Ethylene C₆ C₈ C₁₀ C₁₂ C₁₄ C₁₆+ Conversion (g) (g) (g) (g) (g)(g) (mol %) 46.35 58.91 2.79 3.19 1.67 3.06 4.2 Total C₆-C₈ TotalC₁₀-C₁₄ 105.26 g 7.65 g

TABLE 2 Measured Skewed Skewed Alkene/Alkane Distribution Cyclic Linear1-decene 19 16 21 3-decene 1 0 1 4-decene 3 6 3 5-decene n-decane 7 2 133-methyl-1-nonene 4 0 5 5-methyl-1-nonene 15 30 4 3-methylnonane 1 0 25-methylnonane 1 0 2 2-ethyl-1-octene 3 1 3 4-ethyl-1-octene 1 4 14-ethyloctane 8 2 10 3-propyl-1-heptene 9 20 3 2-butyl-1-hexene 3 7 14-penten-1-yl-cyclopentane 14 7 18 pentylcyclopentane 11 5 13

TABLE 3 Linear Cyclic Linear Linear Alkene/Alkane Dimer Trimer TrimerPentamer 1 1-decene X X X X 2 3-decene X 3 4-decene X X X 4 5-decene X X5 n-decane X X X 6 3-methyl-1-nonene X 7 5-methyl-1-nonene X X 83-methylnonane X 9 5-methylnonane X 10 2-ethyl-1-octene X 114-ethyl-1-octene X X 12 4-ethyloctane X 13 3-propyl-1-heptene X X 142-butyl-1-hexene X X 15 4-penten-1-yl- X cyclopentane 16pentylcyclopentane X

TABLE 4 Alkene/Alkane Inventive Comparative 1-decene 19 48 n-decane 7 24-penten-1-yl-cyclopentane 14 5 pentylcyclopentane 11 3

TABLE 5 Measured Skewed Skewed Alkene/Alkane Distribution Cyclic Linear1-dodecene 14 12 18 4-dodecene 1 1 2 5-dodecene 6-dodecene n-dodecane 41 12 5-methyl-1-undecene 65 82 22 7-methyl-1-undecene 4-ethyl-1-decene6-ethyl-1-decene 3-propyl-1-nonene 5-propyl-1-nonene 2-butyl-1-octene3-butyl-1-octene 4-butyl-1-octene 5-methylundecane 3 1 8 4-ethyldecane5-ethyldecane 3-propylnonane 5-propylnonane 6-hepten-1-ylcyclopentane 72 20 heptylcyclopentane 6 1 18

TABLE 6 Cyclic Linear Cyclic Linear Linear Alkene/Alkane Trimer TrimerTetramer Tetramer Hexamer 1 1-dodecene X X X X X 2 4-dodecene X X 35-dodecene X X X X 4 6-dodecene X X 5 n-dodecane X X X 65-methyl-1-undecene X X 7 7-methyl-1-undecene X X 8 5-methylundecane X X9 4-ethyl-1-decene X X 10 6-ethyl-1-decene X X 11 4-ethyldecane X X 125-ethyldecane X X 13 3-propyl-1-nonene X X 14 5-propyl-1-nonene X X 153-propylnonane X X 16 5-propylnonane X X 17 2-butyl-1-octene X X X X 183-butyl-1-octene X X 19 4-butyl-1-octene X X 20 6-hepten-1- Xylcyclopentane 21 heptylcyclopentane X

TABLE 7 Alkene/Alkane Inventive Comparative 1-dodecene 14 12 n-dodecane4 10 6-hepten-1-ylcyclopentane 7 1 heptylcyclopentane 6 1

TABLE 8 Measured Skewed Skewed Alkene/Alkane Distribution Cyclic Linear1-tetradecene 21 18 24 6-tetradecene 2 1 3 7-tetradecene n-tetradecane 62 12 7-methyl-1-tridecene 53 75 25 6-ethyl-1-dodecene5-propyl-1-undecene 4-butyl-1-decene 3-pentyl-1-nonene 7-methyltridecane3 1 6 6-ethyldodecane 5-propyl-1-undecane 8-nonen-1-ylcyclopentane 8 216 nonylcyclopentane 7 1 14

TABLE 9 Cyclic Linear Linear Linear Alkene/Alkane Tetramer TetramerPentamer Heptamer 1 1-tetradecene X X X 2 6-tetradecene X X 37-tetradecene X X 4 n-tetradecane X X 5 7-methyl-1- X X tridecene 67-methyltridecane X 7 6-ethyl-1-dodecene X X 8 6-ethyldodecane X 95-propyl-1-undecene X X 10 5-propyl-1-undecane X 11 4-butyl-1-decene X X12 3-pentyl-1-nonene X X 13 8-nonen-1- X ylcyclopentane 14nonylcyclopentane X

TABLE 10 Alkene/Alkane Inventive Comparative 1-tetradecene 21 13n-tetradecane 6 1 8-nonen-1-ylcyclopentane 8 1 nonylcyclopentane 7 1

The invention is described herein with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A composition comprising at least 55 wt. % C₁₀ mono-olefins,the C₁₀ mono-olefins comprising:

i) from 11 to 45 wt. % 1-decene;

ii) at least 0.5 wt. % 2-butyl-1-hexene;

iii) at least 1 wt. % 3-propyl-1-heptene;

iv) from 0.5 to 12 wt. % wt. % 4-ethyl-1-octene;

v) at least 4 wt. % 4-penten-1-yl-cyclopentane; and

vi) from 2 to 40 wt. % 5-methyl-1-nonene.

Aspect 2. The composition defined in aspect 1, wherein the C₁₀mono-olefins comprise any suitable amount of 1-decene or any amountdisclosed herein, e.g., from 12 to 42 wt. %, from 12 to 30 wt. %, from15 to 38 wt. %, from 17 to 35 wt. %, or from 20 to 30 wt. %.

Aspect 3. The composition defined in aspect 1 or 2, wherein the C₁₀mono-olefins comprise any suitable amount of 2-butyl-1-hexene or anyamount disclosed herein, e.g., from 0.5 to 12 wt. %, from 0.75 to 12 wt.%, from 1 to 8 wt. %, or from 2 to 6 wt. %.

Aspect 4. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable amount of3-propyl-1-heptene or any amount disclosed herein, e.g., from 1 to 27wt. %, from 3 to 25 wt. %, from 5 to 22 wt. %, or from 7 to 17 wt. %.

Aspect 5. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable amount of4-ethyl-1-octene or any amount disclosed herein, e.g., from 0.5 to 10wt. %, from 0.75 to 7 wt. %, from 0.75 to 5 wt. %, from 1 to 5 wt. %, orfrom 1 to 4 wt. %.

Aspect 6. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable amount of4-penten-1-yl-cyclopentane or any amount disclosed herein, e.g., from 4to 40 wt. %, from 4 to 37 wt. %, from 5 to 34 wt. %, from 7 to 30 wt. %,or from 10 to 25 wt. %.

Aspect 7. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable amount of5-methyl-1-nonene or any amount disclosed herein, e.g., from 2 to 38 wt.%, from 4 to 40 wt. %, from 4 to 33 wt. %, from 6 to 33 wt. %, or from10 to 28 wt. %.

Aspect 8. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins further comprise any suitable amount of2-ethyl-1-octene or any amount disclosed herein, e.g., from 0.3 to 8 wt.%, from 0.5 to 5 wt. %, from 1 to 5 wt. %, or from 0.8 to 4 wt. %.

Aspect 9. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins further comprise any suitable amount of3-methyl-1-nonene or any amount disclosed herein, e.g., from greaterthan 0 to 10 wt. %, from greater than 0 to 8 wt. %, from greater than 0to 6 wt. %, or from 2 to 7 wt. %.

Aspect 10. The composition defined in any one of the preceding aspects,wherein the composition further comprises any suitable amount ofpentylcyclopentane or any amount disclosed herein, e.g., from 1 to 20wt. %, from 2 to 18 wt. %, from 3 to 15 wt. %, from 5 to 13 wt. %, orfrom 7 to 13 wt. %.

Aspect 11. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable weight ratio of(2-butyl-1-hexene+3-propyl-1-heptene+4-ethyl-1-octene+5-methyl-1-nonene)to 1-decene or any weight ratio disclosed herein, e.g., from 0.2:1 to10:1, from 0.3:1 to 8:1, from 0.35:1 to 6:1, from 0.4:1 to 5:1, or from0.8:1 to 5:1.

Aspect 12. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable weight ratio of4-penten-1-yl-cyclopentane to 1-decene or any weight ratio disclosedherein, e.g., from 0:1:1 to 3:1, from 0.2:1 to 2:1, from 0.2:1 to 1.2:1,from 0.3:1 to 1.5:1, from 0.3:1 to 1:1, or from 0.4:1 to 0.9:1.

Aspect 13. The composition defined in any one of the preceding aspects,wherein the C₁₀ mono-olefins comprise any suitable weight ratio of(2-butyl-1-hexene+3-propyl-1-heptene+4-ethyl-1-octene+5-methyl-1-nonene)to 4-penten-1-yl-cyclopentane or any weight ratio disclosed herein,e.g., from 0.1:1 to 12:1, from 0.4:1 to 10:1, from 4:1 to 10:1, from 6:1to 9:1, from 0.3:1 to 4:1, or from 0.4:1 to 3:1.

Aspect 14. The composition defined in any one of the preceding aspects,wherein the composition comprises any suitable amount of C₁₀mono-olefins or any amount disclosed herein, e.g., from 55 to 98 wt. %,from 70 to 95 wt. %, from 85 to 95 wt. %, from 55 to 85 wt. %, from 60to 92 wt. %, or from 65 to 85 wt. %.

Aspect 15. The composition defined in any one of the preceding aspects,wherein the composition comprises any suitable amount of C₁₀hydrocarbons or any amount disclosed herein, e.g., at least 90 wt. %, atleast 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt.%.

Aspect 16. A composition comprising at least 60 wt. % C₁₂ mono-olefins,the C₁₂ mono-olefins comprising i) at least 8 wt. % 1-dodecene and ii)at least 0.5 wt. % 6-hepten-1-yl-cyclopentane; wherein the compositioncomprises heptylcyclopentane and n-dodecane at a weight ratio ofheptylcyclopentane to n-dodecane from 0:3:1 to 8:1.

Aspect 17. The composition defined in aspect 16, wherein the C₁₂mono-olefins comprise any suitable amount of 1-dodecene or any amountdisclosed herein, e.g., from 8 to 40 wt. %, from 9 to 35 wt. %, from 10to 33 wt. %, from 12 to 29 wt. %, or from 13 to 23 wt. %.

Aspect 18. The composition defined in aspect 16 or 17, wherein the C₁₂mono-olefins further comprise any suitable amount of non-cyclic branchedC₁₂ mono-olefins or any amount disclosed herein, e.g., from 22 to 90 wt.%, from 29 to 88 wt. %, from 60 to 86 wt. %, from 60 to 80 wt. %, from35 to 85 wt. %, from 33 to 50 wt. %, or from 33 to 40 wt. %.

Aspect 19. The composition defined in any one of aspects 16-18, whereinthe non-cyclic branched C₁₂ mono-olefins comprise 5-methyl-1-undecene,7-methyl-1-undecene, 4-ethyl-1-decene, 6-ethyl-1-decene,3-propyl-1-nonene, 5-propyl-1-nonene, 2-butyl-1-octene,3-butyl-1-octene, 4-butyl-1-octene, or any combination thereof.

Aspect 20. The composition defined in any one of aspects 16-19, whereinthe C₁₂ mono-olefins comprise any suitable amount of6-hepten-1-yl-cyclopentane or any amount disclosed herein, e.g., from0.5 to 40 wt. %, from 1 to 35 wt. %, from 2 to 40 wt. %, from 2 to 32wt. %, from 3 to 20 wt. %, or from 4 to 15 wt. %.

Aspect 21. The composition defined in any one of aspects 16-20, whereinthe composition comprises any suitable amount of heptylcyclopentane orany amount disclosed herein, e.g., from 0.25 to 25 wt. %, from 0.5 to 23wt. %, from 1 to 23 wt. %, from 3 to 20 wt. %, from 1 to 18 wt. %, orfrom 3 to 10 wt. %.

Aspect 22. The composition defined in any one of aspects 16-21, whereinthe composition comprises any suitable amount of n-dodecane or anyamount disclosed herein, e.g., from 0.25 to 18 wt. %, from 0.5 to 16 wt.%, from 0.5 to 10 wt. %, from 0.75 to 8 wt. %, from 1 to 12 wt. %, from8 to 14 wt. %, or from 0.75 to 10 wt. %.

Aspect 23. The composition defined in any one of aspects 16-22, whereinthe C₁₂ mono-olefins comprise any suitable weight ratio of 1-dodecene to6-hepten-1-yl-cyclopentane or any weight ratio disclosed herein, e.g.,from 0:4:1 to 12:1, from 0.6 to 10:1, from 0.9:1 to 6:1, or from 1.5:1to 4:1.

Aspect 24. The composition defined in any one of aspects 16-23, whereinthe composition comprises any suitable weight ratio ofheptylcyclopentane to n-dodecane or any weight ratio disclosed herein,e.g., from 0:3:1 to 6:1, from 0.3:1 to 3:1, from 0.5:1 to 5:1, from0.5:1 to 2:1, from 0.8:1 to 8:1, from 0.8:1 to 4:1, or from 0.8:1 to1.8:1.

Aspect 25. The composition defined in any one of aspects 16-24, whereinthe composition comprises any suitable amount of C₁₂ mono-olefins or anyamount disclosed herein, e.g., from 60 to 99 wt. %, from 62 to 97 wt. %,from 70 to 98 wt. %, or from 75 to 95 wt. %.

Aspect 26. The composition defined in any one of aspects 16-25, whereinthe composition comprises any suitable amount of C₁₂ hydrocarbons or anyamount disclosed herein, e.g., at least 90 wt. %, at least 95 wt. %, atleast 96 wt. %, at least 97 wt. %, or at least 98 wt. %.

Aspect 27. A composition comprising at least 60 wt. % C₁₄ mono-olefins,the C₁₄ mono-olefins comprising i) at least 12 wt. % 1-tetradecene andii) at least 0.5 wt. % 8-nonen-1-yl-cyclopentane; wherein thecomposition comprises a total of from 3 to 30 wt. % of n-tetradecane andnonylcyclopentane.

Aspect 28. The composition defined in aspect 27, wherein the C₁₄mono-olefins comprise any suitable amount of 1-tetradecene or any amountdisclosed herein, e.g., from 12 to 50 wt. %, from 14 to 45 wt. %, from15 to 40 wt. %, from 16 to 38 wt. %, from 18 to 36 wt. %, or from 20 to35 wt. %.

Aspect 29. The composition defined in aspect 27 or 28, wherein the C₁₄mono-olefins further comprise any suitable amount of non-cyclic branchedC₁₄ mono-olefins or any amount disclosed herein, e.g., from 25 to 85 wt.%, from 30 to 80 wt. %, from 45 to 80 wt. %, from 55 to 70 wt. %, from36 to 78 wt. %, or from 50 to 75 wt. %.

Aspect 30. The composition defined in any one of aspects 27-29, whereinthe non-cyclic branched C₁₄ mono-olefins comprise 7-methyl-1-tridecene,6-ethyl-1-dodecene, 5-propyl-1-undecene, 4-butyl-1-decene,3-pentyl-1-nonene, or any combination thereof.

Aspect 31. The composition defined in any one of aspects 27-30, whereinthe C₁₄ mono-olefins comprise any suitable amount of8-nonen-1-yl-cyclopentane or any amount disclosed herein, e.g., from 0.5to 30 wt. %, from 0.75 to 28 wt. %, from 1.5 to 26 wt. %, from 2 to 24wt. %, or from 5 to 15 wt. %.

Aspect 32. The composition defined in any one of aspects 27-31, whereinthe composition comprises any suitable amount of nonylcyclopentane orany amount disclosed herein, e.g., from 0.5 to 22 wt. %, from 1 to 20wt. %, from 1 to 14 wt. %, from 1.25 to 18 wt. %, or from 3 to 10 wt. %.

Aspect 33. The composition defined in any one of aspects 27-32, whereinthe composition comprises any suitable amount of n-tetradecane or anyamount disclosed herein, e.g., from 0.5 to 18 wt. %, from 1 to 16 wt. %,from 2 to 12 wt. %, from 1.25 to 15 wt. %, or from 3 to 9 wt. %.

Aspect 34. The composition defined in any one of aspects 27-33, whereinthe C₁₄ mono-olefins comprise any suitable weight ratio of 1-tetradeceneto 8-nonen-1-yl-cyclopentane or any weight ratio disclosed herein, e.g.,from 0:5:1 to 15:1, from 0.75:1 to 12:1, from 1:1 to 10:1, from 1.5:1 to9:1, or from 2:1 to 8:1.

Aspect 35. The composition defined in any one of aspects 27-34, whereinthe composition comprises any suitable total amount of n-tetradecane andnonylcyclopentane or any amount disclosed herein, e.g., from 3 to 28 wt.%, from 3 to 26 wt. %, from 4 to 28 wt. %, from 5 to 25 wt. %, or from 6to 20 wt. %.

Aspect 36. The composition defined in any one of aspects 27-35, whereinthe composition comprises any suitable amount of C₁₄ mono-olefins or anyamount disclosed herein, e.g., from 60 to 99 wt. %, from 68 to 96 wt. %,from 75 to 98 wt. %, or from 75 to 95 wt. %.

Aspect 37. The composition defined in any one of aspects 27-36, whereinthe composition comprises any suitable amount of C₁₄ hydrocarbons or anyamount disclosed herein, e.g., at least 90 wt. %, at least 95 wt. %, atleast 96 wt. %, at least 97 wt. %, or at least 98 wt. %.

Aspect 38. A composition comprising: i) any suitable amount of thecomposition defined in any one of aspects 1-15 disclosed herein, e.g.,from 25 to 47 wt. %, from 30 to 42 wt. %, or from 33 to 39 wt. %; ii)any suitable amount of the composition defined in any one of aspects16-26 disclosed herein, e.g., from 30 to 55 wt. %, from 35 to 47 wt. %,or from 38 to 44 wt. %; and iii) any suitable amount of the compositiondefined in any one of aspects 27-37 disclosed herein, e.g., from 12 to35 wt. %, from 15 to 27 wt. %, from 18 to 24 wt. %.

Aspect 39. The composition defined in aspect 38, wherein the compositioncomprises any suitable amount of C₁₀₋₁₄ mono-olefins or any amountdisclosed herein, e.g., from 60 to 99 wt. %, from 70 to 98 wt. %, from75 to 95 wt. %, or from 80 to 95 wt. %.

Aspect 40. The composition defined in aspect 38 or 39, wherein thecomposition comprises any suitable amount of C₁₀₋₁₄ hydrocarbons or anyamount disclosed herein, e.g., at least 90 wt. %, at least 95 wt. %, atleast 96 wt. %, at least 97 wt. %, or at least 98 wt. %.

Aspect 41. The composition defined in any one of aspects 38-40, whereinthe total amount of the composition defined in any one of aspects 1-15,the composition defined in any one of aspects 16-26, and the compositiondefined in any one of aspects 27-37 is any amount disclosed herein,e.g., at least 95 wt. %, at least 97 wt. %, at least 98 wt. %, at least99 wt. %, or at least 99.5 wt. %.

Aspect 42. A composition comprising: i) any suitable amount of thecomposition defined in any one of aspects 1-15 disclosed herein, e.g.,from 15 to 40 wt. %, from 19 to 35 wt. %, or from 22 to 30 wt. %, ii)any suitable amount of the composition defined in any one of aspects16-26 disclosed herein, e.g., from 19 to 40 wt. %, from 23 to 36 wt. %,or from 27 to 33 wt. %; iii) any suitable amount of the compositiondefined in any one of aspects 27-37 disclosed herein, e.g., from 7 to 25wt. %, from 10 to 22 wt. %, or from 13 to 19 wt. %; and iv) any suitabletotal amount of C₁₆ hydrocarbons and C₁₈ hydrocarbons disclosed herein,e.g., at least 18 wt. %, at least 22 wt. %, at least 25 wt. %, from 18to 40 wt. %, from 22 to 36 wt. %, or from 25 to 33 wt. %.

Aspect 43. The composition defined in aspect 42, wherein the compositioncomprises any suitable amount of C₁₀₋₁₈ mono-olefins or any amountdisclosed herein, e.g., from 60 to 99 wt. %, from 70 to 98 wt. %, from75 to 95 wt. %, or from 80 to 95 wt. %.

Aspect 44. The composition defined in aspect 42 or 43, wherein thecomposition comprises any suitable amount of C₁₀₋₁₈ hydrocarbons or anyamount disclosed herein, e.g., at least 90 wt. %, at least 95 wt. %, atleast 96 wt. %, at least 97 wt. %, or at least 98 wt. %.

Aspect 45. The composition defined in any one of aspects 42-44, whereinthe total amount of the composition defined in any one of aspects 1-15,the composition defined in any one of aspects 16-26, the compositiondefined in any one of aspects 27-37, C₁₆ hydrocarbons, and C₁₈hydrocarbons is any amount disclosed herein, e.g., at least 95 wt. %, atleast 97 wt. %, at least 98 wt. %, at least 99 wt. %, or at least 99.5wt. %.

Aspect 46. A composition comprising: i) any suitable amount of thecomposition defined in any one of aspects 1-15 disclosed herein, e.g.,from 30 to 60 wt. %, from 35 to 55 wt. %, or from 40 to 50 wt. %; andii) any suitable amount of the composition defined in any one of aspects16-26 disclosed herein, e.g., from 38 to 68 wt. %, from 43 to 63 wt. %,or from 48 to 58 wt. %.

Aspect 47. The composition defined in aspect 46, wherein the compositioncomprises any suitable amount of C₁₀₋₁₂ mono-olefins or any amountdisclosed herein, e.g., from 60 to 99 wt. %, from 70 to 98 wt. %, from75 to 95 wt. %, or from 80 to 95 wt. %.

Aspect 48. The composition defined in aspect 46 or 47, wherein thecomposition comprises any suitable amount of C₁₀₋₁₂ hydrocarbons or anyamount disclosed herein, e.g., at least 90 wt. %, at least 95 wt. %, atleast 96 wt. %, at least 97 wt. %, or at least 98 wt. %.

Aspect 49. The composition defined in any one of aspects 46-48, whereinthe total amount of the composition defined in any one of aspects 1-15,and the composition defined in any one of aspects 16-26 is any amountdisclosed herein, e.g., at least 95 wt. %, at least 97 wt. %, at least98 wt. %, at least 99 wt. %, or at least 99.5 wt. %.

Aspect 50. A composition comprising: i) any suitable amount of thecomposition defined in any one of aspects 16-26 disclosed herein, e.g.,from 45 to 85 wt. %, from 55 to 75 wt. %, or from 60 to 70 wt. %; andiii) any suitable amount of the composition defined in any one ofaspects 27-37 disclosed herein, e.g., from 20 to 50 wt. %, from 25 to 45wt. %, or from 30 to 40 wt. %.

Aspect 51. The composition defined in aspect 50, wherein the compositioncomprises any suitable amount of C₁₂-14 mono-olefins or any amountdisclosed herein, e.g., from 60 to 99 wt. %, from 70 to 98 wt. %, from75 to 95 wt. %, or from 80 to 95 wt. %.

Aspect 52. The composition defined in aspect 50 or 51, wherein thecomposition comprises any suitable amount of C₁₂-14 hydrocarbons or anyamount disclosed herein, e.g., at least 90 wt. %, at least 95 wt. %, atleast 96 wt. %, at least 97 wt. %, or at least 98 wt. %.

Aspect 53. The composition defined in any one of aspects 50-52, whereinthe total amount of the composition defined in any one of aspects 16-26and the composition defined in any one of aspects 27-37 is any amountdisclosed herein, e.g., at least 95 wt. %, at least 97 wt. %, at least98 wt. %, at least 99 wt. %, or at least 99.5 wt. %.

What is claimed is:
 1. A composition comprising at least 55 wt. % C₁₀mono-olefins, the C₁₀ mono-olefins comprising: i) from 11 to 45 wt. %1-decene; ii) at least 0.5 wt. % 2-butyl-1-hexene; iii) at least 1 wt. %3-propyl-1-heptene; iv) from 0.5 to 12 wt. % wt. % 4-ethyl-1-octene; v)at least 4 wt. % 4-penten-1-yl-cyclopentane; and vi) from 2 to 40 wt. %5-methyl-1-nonene.
 2. The composition of claim 1, wherein the C₁₀mono-olefins comprise from 17 to 35 wt. % 1-decene.
 3. The compositionof claim 1, wherein the C₁₀ mono-olefins comprise from 0.75 to 7 wt. %4-ethyl-1-octene.
 4. The composition of claim 1, wherein the C₁₀mono-olefins comprise a weight ratio of 4-penten-1-yl-cyclopentane to1-decene from 0.3:1 to 1.5:1.
 5. The composition of claim 1, wherein thecomposition comprises: from 60 to 92 wt. % C₁₀ mono-olefins; and from 3to 15 wt. % pentylcyclopentane.
 6. The composition of claim 5, whereinthe C₁₀ mono-olefins comprise: from 1 to 8 wt. % 2-butyl-1-hexene; from3 to 25 wt. % 3-propyl-1-heptene; from 7 to 30 wt. %4-penten-1-yl-cyclopentane; and from 6 to 33 wt. % 5-methyl-1-nonene. 7.A composition comprising at least 60 wt. % C₁₂ mono-olefins, the C₁₂mono-olefins comprising: i) at least 8 wt. % 1-dodecene; and ii) atleast 0.5 wt. % 6-hepten-1-yl-cyclopentane; wherein the compositionfurther comprises heptylcyclopentane and n-dodecane at a weight ratio ofheptylcyclopentane to n-dodecane from 0:3:1 to 8:1.
 8. The compositionof claim 7, wherein the C₁₂ mono-olefins comprise: from 10 to 33 wt. %of 1-dodecene; and from 2 to 32 wt. % 6-hepten-1-yl-cyclopentane.
 9. Thecomposition of claim 7, wherein: the C₁₂ mono-olefins further comprisefrom 29 to 88 wt. % non-cyclic branched C₁₂ mono-olefins; and thenon-cyclic branched C₁₂ mono-olefins comprise 5-methyl-1-undecene,7-methyl-1-undecene, 4-ethyl-1-decene, 6-ethyl-1-decene,3-propyl-1-nonene, 5-propyl-1-nonene, 2-butyl-1-octene,3-butyl-1-octene, 4-butyl-1-octene, or any combination thereof.
 10. Thecomposition of claim 7, wherein: the composition comprises from 62 to 97wt. % C₁₂ mono-olefins; and the weight ratio of heptylcyclopentane ton-dodecane is from 0.5:1 to 2:1.
 11. The composition of claim 10,wherein the C₁₂ mono-olefins comprise a weight ratio of 1-dodecene to6-hepten-1-yl-cyclopentane from 0.9:1 to 6:1.
 12. A compositioncomprising at least 60 wt. % C₁₄ mono-olefins, the C₁₄ mono-olefinscomprising: i) at least 12 wt. % 1-tetradecene; and ii) at least 0.5 wt.% 8-nonen-1-yl-cyclopentane; wherein the composition further comprises atotal of from 3 to 30 wt. % of n-tetradecane and nonylcyclopentane. 13.The composition of claim 12, wherein the composition comprises a totalof from 5 to 25 wt. % n-tetradecane and nonylcyclopentane.
 14. Thecomposition of claim 12, wherein the C₁₄ mono-olefins comprise: from 16to 38 wt. % 1-tetradecene; and from 2 to 24 wt. %8-nonen-1-yl-cyclopentane.
 15. The composition of claim 12, wherein: theC₁₄ mono-olefins further comprise from 30 to 80 wt. % non-cyclicbranched C₁₄ mono-olefins; and the non-cyclic branched C₁₄ mono-olefinscomprise 7-methyl-1-tridecene, 6-ethyl-1-dodecene, 5-propyl-1-undecene,4-butyl-1-decene, 3-pentyl-1-nonene, or any combination thereof.
 16. Thecomposition of claim 12, wherein: the composition comprises from 60 to99 wt. % C₁₄ mono-olefins; and a weight ratio of 1-tetradecene to8-nonen-1-yl-cyclopentane is from 1:1 to 10:1.
 17. A compositioncomprising: (a) a C₁₀ composition comprising at least 55 wt. % C₁₀mono-olefins, the C₁₀ mono-olefins comprising: i) from 11 to 45 wt. %1-decene; ii) at least 0.5 wt. % 2-butyl-1-hexene; iii) at least 1 wt. %3-propyl-1-heptene; iv) from 0.5 to 12 wt. % wt. % 4-ethyl-1-octene; v)at least 4 wt. % 4-penten-1-yl-cyclopentane; and vi) from 2 to 40 wt. %5-methyl-1-nonene; (b) a C₁₂ composition comprising at least 60 wt. %C₁₂ mono-olefins, the C₁₂ mono-olefins comprising: i) at least 8 wt. %1-dodecene; and ii) at least 0.5 wt. % 6-hepten-1-yl-cyclopentane;wherein the composition further comprises heptylcyclopentane andn-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from0:3:1 to 8:1; and (c) a C₁₄ composition comprising at least 60 wt. % C₁₄mono-olefins, the C₁₄ mono-olefins comprising: i) at least 12 wt. %1-tetradecene; and ii) at least 0.5 wt. % 8-nonen-1-yl-cyclopentane;wherein the composition further comprises a total of from 3 to 30 wt. %of n-tetradecane and nonylcyclopentane.
 18. The composition of claim 17,wherein the composition comprises: from 25 to 47 wt. % of the C₁₀composition; from 30 to 55 wt. % of the C₁₂ composition; and from 12 to35 wt. % of the C₁₄ composition.
 19. The composition of claim 18,wherein the composition comprises from 75 to 95 wt. % of C₁₀₋₁₄mono-olefins.
 20. The composition of claim 17, further comprising C₁₆₋₁₈hydrocarbons.
 21. The composition of claim 20, wherein: the compositioncomprises from 75 to 95 wt. % of C₁₀₋₁₈ mono-olefins; and thecomposition comprises: from 15 to 40 wt. % of the C₁₀ composition; from19 to 40 wt. % of the C₁₂ composition; from 7 to 25 wt. % of the C₁₄composition; and from 18 to 40 wt. % of C₁₆₋₁₈ hydrocarbons.